1-(Polyhaloakylthio) indazoles as fungicidal and bactericidal agents

ABSTRACT

Indazoles of the formula:   WHEREIN A IS 1 OR 2, B IS 3 WHEN A IS 1 AND IS FROM 3 TO 5 WHEN A IS 2, X is halogen of atomic number from 17 to 35 with at least one X being bonded to the carbon atom which is bonded to the sulfur atom, Y is halogen of atomic number from 17 to 35 or nitro in positions 4 to 6 of the indazole nucleus and n is an integer from 0 to 1. These compounds are fungicidal and bactericidal.

United States Patent 1191 Fenyes [451 Feb. 18, 1975 1 1 l-(POLYHALOAKYLTHIO) INDAZOLES AS FUNGICIDAL AND BACTERICIDAL AGENTS [75] Inventor: Joseph G. E. Fenyes, Oakland, Calif.

[73] Assignee: Chevron Research Company, San

Francisco, Calif.

22 Filed: Dec. 21, 1967 21 Appl. No.: 705,586

Related U.S. Application Data [62] Division of Ser. No. 579,512, Sept. 15, 1966, Pat.

3,178,447 4/1965 Kohn 260/3095 Primary ExaminerFrederick E. Waddell Attorney, Agent, or Firm-G. F. Magdeburger; John Stoner, Jr.; Raymond Owyang [57] ABSTRACT lndazoles of the formula:

I (YE-E i v u a b (2a-b+1) wherein a is l or 2, b is 3 when a is 1 and is from 3 to 5 when a is 2, X is halogen of atomic number from 17 to 35 with at least one X being bonded to the carbon atom which is bonded to the sulfur atom, Y is halogen of atomic number from 17 to 35 or nitro in positions 4 to 6 of the indazole nucleus and n is an integer from 0 to 1. These compounds are fungicidal and bactericida1 10 Claims, N0 Drawings 1 l-(PQLYHALOAKYLTHIQ) INDAZMOLVES As FUNGICIDAL AND BACTERICIDAL AGENTS cRoss REFERENCE TO RELATED APPLICATIONS This application is a divisional of copending application Ser. No. 579,512, filedSept. 15, 1966, now US. Pat. No. 3,647,818.

This invention is directed to l-(polyhaloalkylthio) indazoles and their use as pesticides.

The unique indazoles of this invention ar 1- polyhaloalkylthio indazoles in which the polyhaloalkylthio group contains 1 to 2 carbon atoms and has 3 to 5 halogens of atomic number of 17 to 35, i.e., chlorine or bromine, at least one of said halogens being bonded to the carbon atom which is bonded to the su1 fur and the indazole nucleus has to 1 nitro or halogen substituents in positions 4 to 6 of the indazole nucleus. These compounds may be represented by the general formula wherein a is 1 or 2, b is 3 when a is l and is from 3 to when a is 2, X is halogen of atomic number from 17 to 35 with at least one X being bonded to the carbon atom which is bonded to the sulfur atom, Y is halogen of atomic number from 17 to 35 or nitro in positions 4 to 6 of the indazole nucleus and n is an integer from 0 to l. Preferably, X is chlorine, a is 2 and b is 4.

Examples of compounds having the above formula are l-(trichloromethylthio) indazole, 1- (tribromomethylthio) indazole, l-(trichloromethylthio)-4-nitroindazo1e, l-(trichloromethylthio)-5- chloroindazole, l-( l ',2'-dibromo-1,2'- dichloroethylthio) indazole, l-(perchloroethylthio) indazole, l-( 1 ',2',2'-trichloroethylthio) indazole, l- (l,l ',2,2'-tetrachloroethylthio) indazole, 1-(l',1,2'-

tribromoethylthio) indazole, l-(l',1,2',2- tetrachloroethylthio )-5-nitroindazole, l-( l ,1 ,2,2- tetrachloroethylthio)-6-bromoindazole and l- (1',l ,2,2'-tetrachloroethylthio)-4chloroindazole.

These novel indazoles may be made by reacting an appropriate polyhaloalkylsulfenyl halide with indazole or a suitably substituted indazole. If desired, the alkali metal salt of indazole may be used. The reaction may be carried out in an aqueous medium or in an organic solvent such as ether, hexane or benzene. If an organic solvent is used, a hydrogen halide acceptor, such as a tertiary amine, must be present. The 1- (polyhaloalkylthio) indazole may be separated from the reaction mixture by conventional methods such as recrystallization. They are solids which are soluble in organic solvents such as acetone, benzene, ether and the like.

The following examples illustrate specific methods by which the compounds of this invention may be prepared. These examples are offered as illustrative only and are not meant to limit the invention as described herein. Unless otherwise indicated, percentages are by weight.

EXAMPLE 1 8.1 g. of 5-nitroindazole, 10.0 ml. of 1.1,2,2- tetrachloroethylsulfenyl chloride and 100 ml. chloroform were added to 50 ml. water in a flask. 5 ml. of acetone were added to this mixture and it was stirred at room temperature for about 18-19 hours. The aqueous layer was then separated from the organic layer and discarded. The organic layer was washed consecutively with dilute aqueous hydrochloric acid and water and then dried over anhydrous magnesium sulfate. The solution was then filtered and stripped under reduced pressure. The solid residue was washed with hexane and then dried to give 16.5 g. of l-(l',l,2,2'- tetrachloroethylthio)-5-nitroindazo1e. This compound melted at l2ll23C. and had the following analysis: Found-Cl 40.1%, S 8.55%; Calculated-Cl 39.28%. S 8.88%.

EXAMPLE 2 Using the general method described in Example 1, 1-(1',1',2,2-tetrachloroethylthio)-6-nitroindazole was prepared using 6-nitroindaz0le instead of 5- nitroindazole. This compound melted at l25-127C. and had the following analysis: Found-Cl 38.75%, S 8.73%; Calculated-Cl 39.28%, S 8.88%.

EXAMPLE 3 By the general method described in Example 1, l- (1',l ,2',Zf-tetrachloroethylthio)-5-chloroindazole was prepared using 5-chloroindazole instead of 5- nitroindazole. It melted at 97-98.5C. and had the following analysis: Found-Cl. 50.70%, S 9.88%; Calculated-Cl. 50.58%, S 9.15%.

EXAMPLE 4 under reduced pressure. A solid formed. It was washed with mixed hexanes and then dried to give 5.5 g. 1- (trichloromethylthio)-5-chloroindazole. lt melted at l03105C. and had the following analsis: Found-Cl 47.15%, 5 10.62%; Calculated-Cl 46.96%, 5 10.60%.

The indazoles of this invention have excellent biological activity, especially against fungi and bacteria. As a group their activity is in general superior to N- polyhaloalkylthio pyrazoles.

lndazoles of this invention were tested as fungicides by means of the mycelial drop test. This test measures the fungitoxicity of a compound in terms of its inhibition of fungus mycelial growth. Each indazole was dissolved in acetone to a 500 ppm concentration. Equal volumes of this solution were applied to the centers of each of three replicate paper discs inoculated with the desired fungus mycelium and placed on potatogicidal activity of the indazole was determined by comparing the radii of mycelial growth away from the edges of the treated and control discs. From this comparison a percent inhibition based on the relative mycelial hosts these pathogens. They may be applied with appropriate inert carriers and diluents as powders, solutions or dispersions. Pesticidal formulations of these indazoles may also contain stabilizers, spreading agents,

growth areas was determined. The results of these tests 5 wetting agents, stickers and other compatible pestiare reported in Table I. cides.

TABLE I lnhibition Pythlum Helminthosporium Fusarium Rhizoctonia Compound Ultimum sativum oxysporum solani l-( I,l '.2.2'Jetrachloroethylthio)- I I00 I00 I00 h-nitroindazole l-( I ,l '.2'.2'-tetrachloroethylthio)- 97 I00 98 I00 -chlomindazole l-( I'.l .2'.2'-tetrachloroethylthio)- I00 I00 I00 I00 5-nitroiudazole l-l lrichluromethylthio )-5-chloro- I00 I00 7 8 I00 indazole lndazoles of this invention were also tested as bacte- I l i ricides. The test method involved contacting a dilute bacterial suspension with the indazole in an aqueous bacterial medium and was carried out as follows: Bacterial medium was made by mixing 21.5 g. dehydrated Emersons Broth (beef peptone, glysate, sodium chloride, yeast extract and dextrose) in 900 ml. distilled water. The bacterial suspension was made by preparing 21.5 g. dehydrated Emersons Broth in one I. distilled water, inoculating the broth with the desired bacteria, incubating the culture and diluting the broth culture tenfold with sterilized water. 9.0 ml. of the medium was put in a vial. The vial was capped and autoclaved at 17 psi for 20 minutes to ensure aseptic conditions. 0.9 ml. of bacterial suspension diluted with water to the same turbidity (measured with a spectrophotometer) as the medium and 50 ml. of an acetone solution of the indazole at the desired concentration were added to the vial.

The vial's contents were then incubated at 2324C. for 40-48 hours. Photometric readings of the vial were made after this period to determine the turbidity of the vial. Similar readings were made on an untreated control sample.- Percent inhibition of bacterial growth was 5 determined by the following formula lnhibition light blocked on test/% light l. A fungicidal composition comprising a fungitoxic eme tvqf an. ind a of e f msl mm wherein a is 1 or 2, b is 3 when a is l and is from 3 to 5 when a is 2, X is halogen of atomic number from 17 to 35 with at least one X being bonded to the carbon atom which is bonded to the sulfur atom, Y is halogen of atomic number from 17 to 35 in positions 4 to 6 of the indazole nucleus and n is an integer from O to l and an inert carrier therefor.

2. A method for controlling fungi which comprises applying a fungitoxic amount of an indazole of the'formula blocked on control) X I00 H The test results are reported in Table II. N Exb (2a-b+l) TABLE ll Compound Concentration lnhibition ppm A C E P l-( l ,l '.2,2'-tetrachloroethylthi0 6-nitro indazole I0 I00 I00 100 100 3 97 I00 I00 96 l 83 82 I7 76 l-( l'.l ',2.2-tetrachloroethylthio)- I0 I00 I00 I00 5-nilro indazole 3 I00 I00 I00 96 I 83 63 89 85 A Agrulmeteria lumul'ueiens (urynuhacteriu miehiguueusu I: Ilrwinin cannm'ma I lsuutlumnnax syringae Aside from the specific methods shown above, these indazoles may be applied by conventional methods in fungitoxic and bactericidally effective amounts to fungal and bacterial pathogens or to environments which wherein a is l or 2, b is 3 when a is l and is from 3 to 5 when a is 2, X is halogen of atomic number from I7 to 35 with at least one X being bonded to the carbon atom which is bonded to the sulfur atom, Y is halogen wherein u is l or 2, I; is 3 when a is l and is from 3 to 5 when a is 2, X is halogen of atomic number from 17 to 35 with at least one X being bonded to the carbon atom which is bonded to the sulfur atom, Y is halogen of atomic number from 17 to 35 in positions 4 to 6 of the indazole nucleus and n is an integer from 0 to l to said bacteria.

4. The fungicidal composition of claim I wherein X is chlorine, a is l or 2 and b is 3 when a is l and 4 when a is 2.

5. The method of claim 2 wherein X is chlorine, a is lor2andbis3whenais l and4whenais2.

6. The method of claim 3 wherein X is chlorine, a is lor2andbis3whenais l and4whenais2.

7. The fungicidal composition of claim 1 wherein a is 2, b is 4, X is chlorine, n is l and Y is chlorine in position 5.

8. The method of claim 2 wherein a is 2, b is 4, X is chlorine, n is l and Y is chlorine in position 5.

9. The method of claim 3 wherein a is 2, b is 4, X is chlorine, n is l and Y is chlorine in position 5.

10. A fungicidal composition comprising a fungitoxic amount of l-(1',l ',2',2'-tctrachloroethylthio)-5- chloroindazole and an inert carrier therefor. 

1. A FUNGICIDAL COMPOSITION COMPRISING A FUNGITOXIC AMOUNT OF AN INDAZOLE OF THE FORMULA
 2. A method for controLling fungi which comprises applying a fungitoxic amount of an indazole of the formula
 3. A method for controlling bacteria which comprises applying a bactericidally effective amount of an indazole of the formula
 4. The fungicidal composition of claim 1 wherein X is chlorine, a is 1 or 2 and b is 3 when a is 1 and 4 when a is
 2. 5. The method of claim 2 wherein X is chlorine, a is 1 or 2 and b is 3 when a is 1 and 4 when a is
 2. 6. The method of claim 3 wherein X is chlorine, a is 1 or 2 and b is 3 when a is 1 and 4 when a is
 2. 7. The fungicidal composition of claim 1 wherein a is 2, b is 4, X is chlorine, n is 1 and Y is chlorine in position
 5. 8. The method of claim 2 wherein a is 2, b is 4, X is chlorine, n is 1 and Y is chlorine in position
 5. 9. The method of claim 3 wherein a is 2, b is 4, X is chlorine, n is 1 and Y is chlorine in position
 5. 10. A fungicidal composition comprising a fungitoxic amount of 1-(1'',1'',2'',2''-tetrachloroethylthio)-5-chloroindazole and an inert carrier therefor. 